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EP2308596B1 - Cu/Zeolith SCR Katalysator zur NOx Reduzierung in Abgasen und Verfahren zu deren Herstellung - Google Patents

Cu/Zeolith SCR Katalysator zur NOx Reduzierung in Abgasen und Verfahren zu deren Herstellung Download PDF

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Publication number
EP2308596B1
EP2308596B1 EP09172402.1A EP09172402A EP2308596B1 EP 2308596 B1 EP2308596 B1 EP 2308596B1 EP 09172402 A EP09172402 A EP 09172402A EP 2308596 B1 EP2308596 B1 EP 2308596B1
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Prior art keywords
zeolite
catalyst
copper
solution
ion
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EP2308596A1 (de
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Robert Ukropec
Albert Chigapov
Alexei Dubkov
Mario Balenovic
Martina Reichert
Brendan Carberry
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Ford Global Technologies LLC
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Ford Global Technologies LLC
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B01J29/072—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/204—Alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/204—Alkaline earth metals
    • B01D2255/2045—Calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/204—Alkaline earth metals
    • B01D2255/2047—Magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2063—Lanthanum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2066—Praseodymium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20715—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—Other metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment

Definitions

  • the present invention basically relates to the abatement of nitrogen oxides (NO x ) and particularly to Selective Catalytic Reduction (SCR) of NO x from exhaust gas streams using ammonia as a reductant.
  • SCR Selective Catalytic Reduction
  • the invention is further related to obtain a SCR catalyst with improved catalyst activity within wide temperature range, and to a method of the catalyst preparation for NO x removal or reduction, combined with reduced emissions of non-reacted ammonia (so called ammonia slip), and reduced side products such as nitrous oxide (N 2 O).
  • the invention relates in particular to a process for reducing NO x from oxygen containing exhaust gases from internal combustion engines (ICE), especially diesel engines, and could be also related to removing process of NO x formed by any other combustion processes, such as in stationary engines, in industry etc via selective catalytic reduction (SCR) of NO x with ammonia (NH 3 ) used as a reducing agent.
  • ICE internal combustion engines
  • SCR selective catalytic reduction
  • Nitrogen oxides are generally recognized as major air pollutants contributing to the formation of acid rain, urban smoke (particularly responsible for ozone formation in the low levels of atmosphere close to urban areas), and global warming via greenhouse effect caused by N 2 O. Their presence in the atmosphere is causing devastating impact on forests and health of people and the living species. It has an enhanced eroding effects on buildings as well.
  • the major sources of the NO x are combustion processes, as an example the internal combustion engine, coal, oil, and gas burners, boilers and incinerators, where NO x forms in the high temperature zones.
  • ammonia is a toxic substance, which is under strong emission legislation standards.
  • N 2 O is a greenhouse gas, and although N 2 O emissions are not yet under the legislation, its greenhouse gas effect (GWP) is 310 times higher compared to CO 2 , which is a major manmade contributor to the global warming.
  • SCR catalyst has its ability to provide high NO x reduction within wide range of exhaust gas flow rates, e.g. under high gas space velocity per hour (GHSV).
  • GHSV gas space velocity per hour
  • the best SCR catalysts developed at the moment include as a basic component copper (Cu) or iron (Fe) - ion-exchanged zeolites.
  • EP 0 393 905 B1 and US 5 024 981 describe SCR catalysts including transition metals-substituted zeolite catalysts, using various zeolites substituted with metals like Cu or Fe.
  • Copper-containing zeolites are more active at low temperatures, less vulnerable to NO/NO 2 ratio and are quite active even with low NO 2 level.
  • they have the following disadvantages: low conversion at high-temperature conditions above 400°C due to the high rate of ammonia oxidation and higher level of N 2 O production.
  • iron-containing systems are good at high-temperature conditions and revealed quite limited level of N 2 O emissions.
  • they are not effective at low temperatures below 300°C and at low level of NO 2 in NO x , which is usual for engines with internal combustion.
  • Another disadvantage of iron-containing zeolites is ammonia slip.
  • US 4 220 632 A discloses the catalytic reduction of NO x in an exhaust gas stream using ammonia as a reductant in the presence of a zeolite catalyst in the hydrogen or sodium form, having pore openings of about 3 to 10 Angstroms.
  • US 4 778 665 A describes an SCR process for pre-treating industrial exhaust gases contaminated with NO x in which the catalyst includes an intermediate pore zeolite (ZSM-5) with a silica to alumina ratio of at least 50.
  • ZSM-5 intermediate pore zeolite
  • the zeolite is preferably in the hydrogen form, or has up to about 1 percent of a platinum group metal (PGM).
  • PGM platinum group metal
  • the hydrogen forms of zeolite ZSM-5 catalyses the SCR reaction at temperatures between about 400°C to about 500°C.
  • US 5 520 895 A describes a process employing iron impregnated zeolites as catalysts for the SCR of NOx in the exhaust gas. These catalysts are capable to obtain more than 80 percent conversion of the NO x and have been tested as powders at GHSV of 12000 h -1 .
  • WO 2008085280 describes the catalysts containing zeolite and different metal ions, basically cerium, which are displaying good high-temperature performance, but such catalysts are not active below 300 °C.
  • the present invention is dealing with these mentioned disadvantages and it is focused on improvement of SCR catalyst performance to be active in NOx reduction within wide temperature range using NO-only reaction mixtures under any Diesel exhaust operating conditions and under high space velocities, with decreased NH 3 slip and N 2 O emissions and increased thermal stability up to 900°C under hydrothermal conditions, which are typical for automotive exhaust conditions.
  • the performance of Cu/zeolite commercial catalysts can be greatly improved at high temperatures to provide NOx conversion near and above 80% at 200-600°C, and more than 90% NO x conversion from 250°C up to 600°C.
  • This new catalyst has also very high resistance to thermal deactivation in comparison with commercial Cu/zeolite catalyst even after hydrothermal treatment at 900°C.
  • This method comprises first a removal, in a starting material of honeycomb structure that is Cu-ZSM-5 zeolite washcoated on a monolithic substrate, of copper and of aluminum extra-lattice species from the zeolite.
  • This first step is performed by double treatment with a citrate-containing solution, whereby the first treatment is followed by intermediate calcination at a temperature of at least 500°C and wherein the second treatment with the citrate-containing solution is carried out after said calcination.
  • the intermediated calcination is necessary to dealuminate zeolite with formation of extra-framework aluminum species in zeolite channels and to re-distribute remaining copper ions to facilitate their removal.
  • the following second treatment with citric acid - diammonium citrate salt is designed to finally remove the formed extra-framework aluminum and remaining copper species.
  • the second step includes re-insertion of copper or insertion of Cu-M ions, where M can be selected from the group consisting of Mg, Ca, Sr, La, Pr, B, Zr or Mg-Fe or Mg-Ce, by ion-exchange and/or impregnation of the washcoated zeolite from which copper and aluminum extra-lattice species have been removed.
  • the second step is preferably including the ion-exchange of modified zeolite with a solution of copper nitrate or with a mixture of copper nitrate and magnesium nitrate.
  • These mixed Cu-M/zeolite - as an example Cu-Mg/zeolite - catalysts can be also produced during the second step by ion-exchange with copper nitrate with the following impregnation with magnesium nitrate in the presence of urea.
  • the following promoters such as Ca, Sr, La, Pr, B, Zr, can be used instead of magnesium.
  • Magnesia can be partially substituted by Fe or Ce. These promoters are in place to protect zeolite from new dealumination with formation of new extra-framework aluminum species.
  • the catalysts described in this invention are monolith type commercial materials of honeycomb structure consisting from a substrate washcoated with zeolite-containing catalyst material.
  • the substrate can be made from refractory materials such as a ceramic, e.g. cordierite, but could also be made from metals, or could be made from the materials containing catalytic material, namely zeolite via extruding it as a monolith.
  • the catalytic washcoat is based on zeolites or could be based on any other silica-alumina microporous materials, such as for example silica-alumina phosphates (SAPO).
  • SAPO silica-alumina phosphates
  • Such modified Cu-M/zeolite can be also used for applications with Diesel particulate filter, including Cu-M/zeolite SCR catalyst deposited on the filter and for applications with SCR catalyst downstream (behind) of the DPF due to their extremely high thermal stability.
  • the modified Cu/zeolite or Cu/M catalyst prepared according to this invention has high NO x reduction properties at temperatures of 170-600°C and increased hydrothermal stability up to 900°C.
  • a core catalyst sample of 3 ⁇ 4" D x 1 "L was inserted into quartz tube wrapped with a matting material.
  • the cores were equipped with two thermocouples inserted directly before and behind core sample.
  • a conventional flow setup was used for gas mixture preparation. All gases were of ultra high purity. Humidifier was installed to provide precise water concentration in the gas line. The flow rates were controlled using mass flow controllers (MKS, Kunststoff, Germany). To prevent water condensation, all connection lines were heated up to app. 170°C. Reactor effluents were analyzed with Twin Chemical Ionization MS from MS4, Austria.
  • the concentration of NO x in the gas mixture for experiments was 500 ppm, NH 3 600 ppm, O 2 10 vol. %, and H 2 O 10%, and helium as balance. Typically 500 ppm of NO represented NO x for experiments. Total feed flows were set to obtain SV 30000; 60000 or 90000 h -1 .
  • the preparation process for the individual samples was as follows: Commercially available samples containing copper (commercial Cu-zeolite, Reference 1 ) and iron (commercial Fe-zeolite, Reference 2 ) ZSM-5 zeolite were used as the reference samples and for preparation of modified samples, presenting this invention. All reference samples were zeolite-washcoated cordierite with small amount of alumina as a binder.
  • All reference samples were zeolite-washcoated cordierite with small amount of alumina as a binder.
  • Example 1 Invention - Cu/ citrate treated zeolite
  • the cores were treated further the second time under the same conditions with the same solution containing citric acid and its diammonium hydrogen salt, washed with distilled water using a big excess of water and were then dried at 100°C and calcined at 400°C.
  • the core samples were prepared and treated as in example 1, but were ion-exchanged with the solution containing mixture of copper and magnesium nitrates instead of only copper nitrate as in example 1.
  • the cores were prepared according to Example 1, including the ion-exchange with copper nitrate under the same conditions.
  • the samples were further dried at 100°C and calcined at 400°C with the following impregnation, using solution of metal salt (salts) in the presence of urea.
  • the samples were dried at 88°C in closed containers overnight and were finally calcined at 600°C for 1 h.
  • Example 3a (Cu-Mg) was impregnated with the solution of 25 mg of magnesium nitrate, 0.6 g of urea and 1.8 g of distilled water per core.
  • Example 3b (Cu-B) was impregnated with the solution of 20 mg of ammonium pentaborate, 0.6 g of urea and 1.8 g of distilled water per core.
  • Example 3c (Cu-La) was impregnated with a solution containing 42 mg of lanthanum nitrate, 0.6 g of urea and 1.8 g of distilled water per core.
  • Example 3d (Cu-Ca) was impregnated with a solution containing 11 mg of calcium nitrate, 0.6 g of urea and 1.8 g of distilled water per core.
  • Example 3e (Cu-Sr) was impregnated with a solution containing 12 mg of strontium nitrate, 0.6 g of urea and 1.8 g of distilled water per core.
  • Example 3f (Cu-Pr) was impregnated with a solution containing 21.7 mg of praseodymium nitrate, 0.6 g of urea and 1.8 g of distilled water per core.
  • Example 3g (Cu-Zr) was impregnated with a solution containing 62 mg of zirconyl nitrate (35 weight% in diluted nitric acid), 0.6 g of urea and 1.8 g of distilled water per core.
  • Example 3h (Cu-Mg-Fe) was impregnated with a solution containing 5 mg of magnesium nitrate; 5 mg of iron (III) nitrate and 0.6 g of urea and 1.8 g of distilled water per core.
  • Example 3i (Cu-Mg-Ce) was impregnated with a solution containing 5 mg of magnesium nitrate; 17 mg of cerium (III) nitrate and 0.6 g of urea and 1.8 g of distilled water per core.
  • the Cu-SCR catalyst has an excellent NO x conversion level within medium temperature range at 200-400°C, which is close to 100% NO x reduction, but NO x conversion decreased at temperatures above 450°C.
  • the performance of commercial Fe/zeolite catalyst is presented on Fig. 1 , too. Iron-containing systems are good under high-temperature conditions in contrast to Cu-containing systems, and revealed a quite limited low level of N 2 O emissions, as can be seen on Fig. 4 , but Fe-SCR catalyst is not effective at low temperatures, and at low levels of NO 2 .
  • Cu- only and Fe-only SCR catalysts have real disadvantages, which do not allow them to provide effective NO x reduction for wide temperature range.
  • Cu-SCR has higher N 2 O selectivity, while Fe-containing SCR has ammonia slip, which is not acceptable.
  • the catalytic activity of these samples also depends on the level of NO 2 in the NO x , which is requiring the specific NO oxidation catalysts upstream of the SCR catalyst.
  • the extra-lattice aluminum species from zeolite can be removed by the treatment with acidic or alkaline solution.
  • commercial Cu/zeolite catalyst is deposited as washcoat on cordierite.
  • the treatment of commercial samples with acidic or basic solution destroys the links (chemical bonds) of washcoat with substrate and leads to removal of zeolite-containing washcoat from substrate.
  • zeolite is connected with cordierite substrate via aluminum oxide binder, and this binder is soluble in strong acids or alkalis. In addition strong acids or alkalis can dissolve zeolite matrix.
  • the other problem was that commercial samples already have copper including copper centers connected with extra-framework aluminum species, so it was necessary to remove not only extra-framework aluminum species, but also copper species from zeolite.
  • this weakly acidic solution is not able to dissolve aluminum binder in washcoat and zeolite lattice, therefore this specific treatment is very selective according to the following scheme: Cu, Al-Zeolite + citric acid, diammonium hydrogen citrate ⁇ Cu, Al ammonium citrate complexes in solution (Reaction 4)
  • oxycarboxylic acids as malic and tartaric acids, and their ammonium salts also can be used to remove Cu and extra-framework aluminum, but they are less effective.
  • the citrate treated zeolite, having decreased amount of copper and extra-lattice aluminum species was further calcined at 600°C.
  • the reason of these calcinations was to form extra-lattice aluminum species again due to dealumination process.
  • These aluminum species come basically from amorphous impurities and defect areas of zeolite structure, where it is enriched by aluminum, especially those zones containing Al-O-Al species.
  • the other reason of intermediate calcinations was to re-distribute the remaining copper species to facilitate their removal, because it is not possible to remove all copper ions by single citrate treatment.
  • citrate treatment can remove extra-lattice (extra-framework) aluminum species, but cannot prevent their new formation, though the amount of new formed extra-framework aluminum species will be definitely lower, because the major part of aluminum from defects, amorphous area and aluminum-enriched zeolite areas has been already removed.
  • zeolite structure from dealumination using additional ions is desirable, as it has been described in our early publication. It may help to further improve the performance of modified citrate-treated Cu/zeolite and may provide in addition the higher thermal stability against high-temperature deactivation. Such additional ions could occupy the same extra-lattice positions, preventing the appearance of aluminum ions on these positions and thus dealumination of zeolite.
  • the amount of additional ions should be kept as low as necessary otherwise the activity of Cu/zeolite will suffer at low temperatures due to the decreased amount of active Cu sites. Such competition between ions will occur also during high temperature calcinations due to the enhanced mobility of ions at these temperatures and small and highly charged ions will have an advantage in this case too, forcing other ions to extra-lattice positions.
  • Example 2 the addition of magnesium ions during ion-exchange with copper nitrate had a big positive effect at low concentrations of magnesium nitrate.
  • the sample 2a was prepared using Cu/Mg ratio of 15 in solution.
  • This sample revealed the same activity as original commercial and Cu-only modified acid-treated zeolite (Example 1) at low temperatures, while NO x conversion was found to be increased up to 85% at near 600°C.
  • This sample can effectively convert NO x with ammonia at all temperature conditions, which are typical for Diesel engine, and under high space velocities.
  • the real Cu/Mg ratio in zeolite is lower, e.g. zeolites enriched with magnesium relative to Cu/Mg ratio in solution due to the preferential ion-exchange of magnesium ions in comparison with copper ions.
  • the increase of magnesium ion concentration in solution during the ion-exchange procedure, and accordingly higher magnesium ion concentration in zeolites leads to the lower performance under the low-temperature conditions as can be seen for Examples 2a-2c, Figure 2 . However, it leads to better and excellent high-temperature performance up to near 100% of NO x conversion at 600°C.
  • ammonia slip properties of the catalyst samples are quite close to that of Cu/zeolite reference sample, except for the samples with high magnesium loading (Cu/Mg 5/1, sample 2c), while N 2 O selectivity is lower. So these catalysts can combine the best properties of Cu/zeolite and Fe/ zeolite reference catalysts.
  • the samples prepared by methods of this invention also have an excellent stability and durability even under severe hydrothermal conditions, which are typical for applications with Diesel particulate filter (DPF).
  • DPF Diesel particulate filter
  • SCR catalyst When SCR catalyst is deposited on the filter or installed downstream of the DPF, it will be exposed to extremely high temperatures during DPF regeneration from soot, up to 800-900°C.
  • the comparison of commercial Cu/zeolite, Reference 1, and Cu-Pr, Example 3f and Cu-Zr, example 3g of the invention, after severe hydrothermal treatment at 900°C is presented on Figure 7 . Both samples had practically kept their low-temperature performance, as can be seen from comparison of Fig.6 and Fig.7 . For samples pictured in Fig.6 , the hydrothermal treatment was carried out only at 600°C.
  • the catalysts of the invention are the first example of SCR catalysts with ammonia as a reductant, showing high performance under whole temperature range operating conditions of Diesel engines in contrast to commercial Cu/zeolite and Fe/zeolite, also combining the best properties of such catalyst regarding ammonia slip and N 2 O formation.
  • the best catalysts of present invention have shown at least the same activity as Cu/zeolite commercial catalyst at low temperatures and the close performance to Fe/zeolite commercial catalyst at high temperatures.
  • the catalysts of present invention can be also used for SCR reactions with other reductants for NOx reduction, for example for SCR with hydrocarbons.

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Claims (13)

  1. Verfahren zum Modifizieren eines Cu/Zeolith-SCR-Katalysators für die selektive katalytische Reduktion von Stickstoffoxiden mit Ammoniak, umfassend gewerblichen Katalysator auf Cordierit oder einem anderen Substrat,
    gekennzeichnet durch folgende Schritte:
    a) aus einem Ausgangsmaterial mit Bienenwabenstruktur, bei dem es sich um Cu-ZSM-5-Zeolith aufgeschichtet auf ein monolithisches Substrat handelt, Entfernen von Kupfer und von Aluminium-Zwischengitterspezies aus dem Zeolith und
    b) Wiedereinführen von Kupfer oder Einführen von Cu-M-Ionen, wobei M ausgewählt sein kann aus der Gruppe bestehend aus Mg, Ca, Sr, La, Pr, B, Zr oder Mg-Fe oder Mg-Ce, durch Ionenaustausch und/oder Imprägnieren des aufgeschichteten Zeoliths, aus dem Kupfer und Aluminium-Zwischengitterspezies entfernt worden sind,
    wobei Schritt a) durch Zweifachbehandlung mit einer citrathaltigen Lösung durchgeführt wird, wobei die erste Behandlung von Zwischenkalzinieren bei einer Temperatur von wenigstens 500 °C gefolgt wird und wobei die zweite Behandlung mit der citrathaltigen Lösung nach der Kalzinierung durchgeführt wird.
  2. Verfahren gemäß Anspruch 1,
    dadurch gekennzeichnet, dass
    die citrathaltige Lösung ein Gemisch von Citronensäure und Diammoniumhydrogencitrat ist.
  3. Verfahren gemäß Anspruch 1 oder 2,
    dadurch gekennzeichnet, dass
    die Zweifachbehandlung mit der citrathaltigen Lösung bei Schritt a) bei einer Temperatur von 80-100 °C, vorzugsweise von 88 °C, durchgeführt wird.
  4. Verfahren gemäß einem der Ansprüche 1 bis 3,
    dadurch gekennzeichnet, dass
    die citrathaltige Lösung für die Zweifachbehandlung bei Schritt a) einen pH-Wert von 4 bis 5 aufweist.
  5. Verfahren gemäß einem der Ansprüche 1 bis 4,
    dadurch gekennzeichnet, dass
    das Wiedereinführen von Kupfer bei Schritt b) unter Verwendung von Ionenaustausch mit einer Lösung von Kupfernitrat, vorzugsweise mit 0,1 M, durchgeführt wird.
  6. Verfahren gemäß einem der Ansprüche 1 bis 4,
    dadurch gekennzeichnet, dass
    das Einführen von Cu-M-Ionen bei Schritt b) mit Mg als anderes Metallion unter Verwendung von Ionenaustausch unter Verwendung einer Lösung von Kupfernitrat mit 0,1 M und Magnesiumnitrat mit einem Cu/Mg-Molverhältnis in Lösung von 30/1 bis 5/1 durchgeführt wird.
  7. Verfahren gemäß einem der Ansprüche 1 bis 4,
    dadurch gekennzeichnet, dass
    das Wiedereinführen von Kupfer oder das Einführen von Cu-M-Ionen bei Schritt b) durch Ionenaustausch unter Verwendung einer Lösung von Kupfernitrat mit 0,1 M, Zwischenkalzinierungen bei einer Temperatur von wenigstens 350 °C, vorzugsweise bei 400 °C, und nachfolgender Imprägnierung mit einer Lösung von Metallsalzen, die
    - ein oder mehrere Kationen aus der folgenden Gruppe enthalten: Mg, Ca, Sr, La, Pr, B, Zr; oder
    - ein Gemisch aus einem Magnesiumsalz und einem Eisen(Fe)-Salz enthalten; oder
    - ein Gemisch aus einem Magnesiumsalz und einem Cer(Ce)-Salz enthalten,
    durchgeführt wird.
  8. Verfahren gemäß Anspruch 7,
    dadurch gekennzeichnet, dass
    das Imprägnieren mit Metallsalz oder Metallsalzen in Gegenwart von Harnstoff durchgeführt wird.
  9. Verfahren gemäß Anspruch 7 oder 8,
    dadurch gekennzeichnet, dass
    der imprägnierte Katalysator über einen Zeitraum von wenigstens 6 Stunden in einem geschlossenen Behälter bei einer Temperatur von 88 °C getrocknet wird, mit nachfolgenden Kalzinierungen bei 600 °C.
  10. Modifizierter Cu/Zeolith- oder Cu-M-ZeolithKatalysator, aufgeschichtet auf ein monolithisches Substrat, für die SCR-Reduktion von NOx in Abgasströmen,
    dadurch gekennzeichnet, dass
    der Katalysator durch die Verfahren gemäß einem der Ansprüche 1 bis 9 erhältlich ist.
  11. Katalytisches Nachbehandlungssystem,
    dadurch gekennzeichnet, dass
    das katalytische Nachbehandlungssystem einen Diesel-Partikelfilter (DPF) und einen SCR-Katalysator mit dem modifizierten Cu/Zeolith oder Cu-M-Zeolith, aufgeschichtet auf ein monolithisches Substrat, gemäß Anspruch 10 stromaufwärts und/oder stromabwärts bezogen auf den DPF angeordnet umfasst.
  12. Katalytisches Nachbehandlungssystem gemäß Anspruch 11,
    dadurch gekennzeichnet, dass
    das System dafür ausgelegt ist, den Abgasen Ammoniak zuzugeben, wobei die Temperatur der Abgase von 100 bis 700 °C variiert, vorzugsweise von 170 bis 600 °C.
  13. Katalytisches Nachbehandlungssystem,
    dadurch gekennzeichnet, dass
    ein Katalysator gemäß Anspruch 10 mit stromaufwärtigen oder stromabwärtigen katalytischen Cu/Zeolith- und/oder Fe/Zeolith-Systemen kombiniert ist.
EP09172402.1A 2009-10-07 2009-10-07 Cu/Zeolith SCR Katalysator zur NOx Reduzierung in Abgasen und Verfahren zu deren Herstellung Not-in-force EP2308596B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP09172402.1A EP2308596B1 (de) 2009-10-07 2009-10-07 Cu/Zeolith SCR Katalysator zur NOx Reduzierung in Abgasen und Verfahren zu deren Herstellung
CN201010509228.5A CN102029175B (zh) 2009-10-07 2010-09-29 选择性催化还原剂及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP09172402.1A EP2308596B1 (de) 2009-10-07 2009-10-07 Cu/Zeolith SCR Katalysator zur NOx Reduzierung in Abgasen und Verfahren zu deren Herstellung

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EP2308596A1 EP2308596A1 (de) 2011-04-13
EP2308596B1 true EP2308596B1 (de) 2016-09-21

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